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Salar Bagherpour
http://dx.doi.org/10.5772/48697
1. Introduction
A composite material is a non uniform solid consisting of two or more different materials
that are mechanically bonded together. Each of the various components retains its identity
in the composite and maintains its characteristic structure and properties. Generally, the
structure of a composite consists of two phases, matrix and reinforcement. The matrix is a
continuous phase and the reinforcement is a discontinuous one. The duty of reinforcements
is attaining strength of the composite and the matrix has the responsibility of bonding of the
reinforcements. There are recognizable interface between the materials of matrix and
reinforcements. The composite materials, however, generally possess combination of
properties such as stiffness, strength, weight, high temperature performance, corrosion
resistance, hardness and conductivity which are not possible with the individual
components. Indeed, composites are produced when two or more materials or phases are
used together to give a combination of properties that cannot be achieved otherwise.
Composite materials especially the fiber reinforced polyester (FRP) kind highlight how
different materials can work in synergy. Analysis of these properties shows that they
depend on (1) the properties of the individual components; (2) the relative amount of
different phases; (3) the orientation of various components; the degree of bonding between
the matrix and the reinforcements and (4) the size, shape and distribution of the
discontinuous phase. The material involves can be organics, metals or ceramics. Therefore, a
wide range of freedom exists, and composite materials can often be designed to meet a
desired set of engineering properties and characteristics [1].
There are many types of composite materials and several methods of classifying them. One
method is based on the matrix materials which include polymers, metals and ceramics. The
other method is based on the reinforcement phase which has the shape of fiber, particulate
and whisker. Whiskers are like fibers but their length is shorter. The bonding between the
particles, fibers or whiskers and the matrix is also very important. In structural composites,
polymeric molecules known as coupling agent are used. These molecules form bonds with
2012 Bagherpour, licensee InTech. This is an open access chapter distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
136 Polyester
the dispersed phase and become integrated into the continuous matrix phase as well. The
most popular type of composite material is the fiber-reinforced polyester composites, in
which continuous thin fibers of one material such as glass, carbon or natural fibers are
embedded in a polyester matrix. They are also called glass fiber reinforced polyester
(GFRP), carbon fiber reinforced polyester (CFRP) and natural fiber reinforced polyester
(NFRP). The objective is usually to enhance strength, stiffness, fatigue, resistance, or
strength to weight ratio by incorporating strong and stiff fibers in a softer, more ductile
matrix. The microstructure of a selected GFRP composite is shown in figure 1.
about the same as the lower grades of the carbon fiber. Other high-strength high-modulus
fibers such as boron are at the present time considered to be economically prohibitive.
There are also the other fiber glasses which are used for FRP reinforcement as well as;
- A-glass, soda lime silicate glasses used where the strength, durability, and good
electrical resistivity of E-glass are not required.
- D-glass, borosilicate glasses with a low dielectric constant for electrical applications.
- ECR-glass, calcium alumino silicate glasses with a maximum alkali content of 2 wt.%
used where strength, electrical resistivity, and acid corrosion resistance are desired.
- AR-glass, alkali resistant glasses composed of alkali zirconium silicates used in cement
substrates and concrete.
- R-glass, calcium alumino silicate glasses used for reinforcement where added strength
and acid corrosion resistance are required.
- S-2-glass, magnesium alumino silicate glasses used for textile substrates or
reinforcement in composite structural applications which require high strength,
modulus, and stability under extreme temperature and corrosive environments.
Table 1 and 2 show the chemical and mechanical properties of different glass fibers
respectively.
The proportion of graphite in a carbon fiber can range from 0 to 100%. When the proportion
is high, the fiber is said to be graphitic, and it is called a graphite fiber. However, a graphite
fiber is polycrystalline, whereas a graphite whisker is a single crystal with the carbon layer
rolled up like a scroll. Because of their single crystal nature, graphite whiskers are virtually
flaw-free and have exceptionally high strength. However, the production yield of graphite
whiskers is too low for them to be commercially significant.
140 Polyester
Commercial carbon fibers are fabricated by using pitch or polyacrylonitrile (PAN) as the
precursor. Precursor fibers are fabricated by conventional spinning techniques, such as wet
spinning for PAN and melt spinning for pitch. They must be converted to a form which is
flameproof and stable at the high temperatures (>700oC) involved in carbonization.
Therefore, before carbonization (pyrolysis), they are stabilized for the case of the PAN
precursor, or infusiblized for the case of the pitch precursor. Both stabilization and
infusiblization are carried out in an oxidizing atmosphere. After that, general-purpose and
high-performance fibers are obtained by carbonization in an inert atmosphere, followed by
graphitization at >2500oC in an inert atmosphere if a high modulus is desired, whereas
activated carbon fibers are obtained by activating in a reactive atmosphere, such as steam at
elevated temperatures. To enhance the preferred orientation in the high-performance carbon
fibers, graphitization can be performed while the fibers are under tension. The higher the
graphitization temperature, the greater the preferred orientation.
For the case of pitch as the precursor, isotropic pitch gives an isotropic carbon fiber, which
belongs to the category of general-purpose carbon fibers, whereas anisotropic pitch (such as
mesophase pitch) gives high-performance carbon fibers which have the carbon layers
preferentially parallel to the fiber axis.
Surface treatments of carbon fibers are essential for improving the bonding between the
fibers and the polymer matrix. They involve oxidation treatments and the use of coupling
agents, wetting agents, and/or sizing (coatings). Carbon fibers need treatment both for
thermosets and thermoplasts. As the processing temperature is usually higher for
thermoplasts than thermosets, the treatment must be stable to a higher temperature (300-
400"C) when a thermoplast is used.
Although there are many carbon fibers available on the open market, they can be arbitrarily
divided into three grades as shown in Table 4. They have lower thermal expansion
coefficients than both the glass and aramid fibers. The carbon fiber is an anisotropic
material, and its transverse modulus is an order of magnitude less than its longitudinal
modulus. The material has a very high fatigue and creep resistance.
Since its tensile strength decreases with increasing modulus, its strain at rupture will also be
much lower. Because of the material brittleness at higher modulus, it becomes critical in
joint and connection details, which can have high stress concentrations. As a result of this
phenomenon, carbon composite laminates are more effective with adhesive bonding that
eliminates mechanical fasteners [5].
Fibre Reinforced Polyester Composites 141
or benzoyl peroxide (BPO) and the amount varies from 1-2%. The catalyst will decompose in
the presence of the polyester resin to form free radicals, which will attack the unsaturated
groups (like C=C) to initiate the polymerization. The processing temperature and the
amount of the catalyst can control the rate of polymerization, the higher temperature or the
more the catalyst, the faster the reaction. After the resin turned from liquid to brittle solid,
post cure at higher temperature may need to be done. The purpose of the post cure is to
increase Tg of the resin by complete cross-linking. The properties of the polyester resin are
affected by the type and amount of reactant, catalyst and monomers as well as the curing
temperature. The higher the molecular weight of polyester and the more points of
unsaturation in molecules, the higher is the strength of the cured resins. Orthophthalic
polyesters are environmentally sensitive and have limited mechanical properties. They have
been replaced in some applications by isophthalic polyesters due to the excellent
environment resistance and improved mechanical properties of the latter.
The unsaturated polyester amounts to about 75% of all polyester resins used in the world. It
is produced by the condensation polymerization of dicarboxylic acids and dihydric alcohols.
The formulation contains an unsaturated material such as maleic anhydride or fumaric acid
which is a part of the dicarboxylic acid component. The formulation affects the viscosity,
reactivity, resiliency and heat deflection temperature (HDT). The viscosity controls the
speed and degree of wet-out (saturation) of the fibers. The reactivity affects cure time and peak
exotherm (heat generation) temperatures. High exotherm is needed for a thin section curing at
room temperature and low exotherm for a thick section. Resiliency or flexible grade
composites have a higher elongation, lower modulus and HDT. The HDT is a short term
thermal property which measures the thermal sensitivity and stability of the resins. The
advantages cited in the unsaturated polyester are its dimensional stability and affordable cost.
Other advantages include ease in handling, processing, and fabricating. Some of the special
formulations are high corrosion resistant and fire retardants. This resin is probably the best
value for a balance between performance and structural capabilities [3,4].
2.2.2. Epoxies
The epoxies used in composites are mainly the glycidyl ethers and amines. The material
properties and cure rates can be formulated to meet the required performance. Epoxies are
generally found in marine, automotive, electrical and appliance applications. The high
viscosity in epoxy resins limits it use to certain processes such as molding, filament winding,
and hand lay-up. The right curing agent should be carefully selected because it will affect
the type of chemical reaction, pot life and final material properties. Although epoxies can be
expensive, it may be worth the cost when high performance is required. Table 6 shows
mechanical properties of polyester and epoxy resins.
styrene monomer to produce vinyl ester resins which are cured with organic peroxides. A
composite product containing a vinyl ester resin can withstand high toughness demand and
offer excellent corrosion resistance [3].
= f . = f + f + + f (1)
= f + f (2)
Where the subscripts m and f refer to the matrix and fiber. Note that fm= 1- ff .
In addition the rule of mixture is used to predict the modulus of elasticity when fibers are
continuous and unidirectional. Parallel to the fibers, the modulus of elasticity may be as
high as:
E = f E + f E (3)
However, when the applied stress is very large, the matrix beings to deform and the stress-
strain curve is no longer linear (figure 3). Since the matrix now contributes little to the
stiffness of the composite, the modulus can be approximated by:
E = f E (4)
Figure 3. The stress strain curve for fiber- Reinforced composite. At low stresses (region ), the
modulus of elasticity is given by the rule of mixtures. At higher stresses (region ), the matrix deforms
and the rule of mixture no linger obeyed.
When the load is applied perpendicular to the fibers, each component of the composite acts
independently of the other. The strain of composite is according to the rule of mixture.
= f + f (5)
=f + f (6)
Fibre Reinforced Polyester Composites 145
Since c=m=f then the modulus of elasticity for perpendicular load applied condition is
according to relation 7 .
= + (7)
,
Tensile strength of FRP composites (TSc) depends on the bonding between the fibers and the
matrix. However, the rule of mixtures is sometimes used to approximate the tensile strength
of a composite containing continuous parallel fibers:
TS = f + f TS (8)
Where TSf is the tensile strength of the fiber and m is the stress acting on the matrix when the
composite is strained to the point where the fiber fractures. Thus, m is not the actual tensile
strength of the matrix. Other properties, such as ductility, impact properties, fatigue
properties, and creep prosperities, are difficult to predict even for unidirectional aligned fibers.
Many factors must be considered when designing a FRP composite, including the length,
diameter, orientation, amount and properties of fibers, matrix and bonding between fibers
and matrix.
In the case of fibers length and diameter it should be considered that fibers can be short,
long or even continuous. Their dimensions are often characterized by the aspect ratio ,
where is the fiber length and is the diameter. Typical fibers have diameter varying from
10 m to 150 m.
The strength of composite improves when the aspect ratio is large. Fibers often fracture
because of surface imperfections. Making the diameter as small as possible gives the fiber
less surface area and, consequently, fewer flaws that might propagate during processing or
under a load. The long fiber is more preferable. The ends of a fiber carry less of the load than
the remainder of the fiber, consequently, the fewer the ends, the higher the load ability of
the fibers (figure 4).
60000
50000
Tensile Strenght (PSI)
40000
30000
20000
10000
0
0 0.5 1 1.5 2 2.5
Glass Fiber Lenght (in)
Figure 4. Increasing the length of chopped E-glass fibers in a polyester matrix increases the strength of
the composite.
146 Polyester
In many FRP systems, discontinuous fibers with an aspect ratio greater than some critical
value are used to provide an acceptable compromise between processing ease and properties.
A critical fiber length for any given fiber diameter can be determined by relation 9.
= (9)
Where TSf is the strength of the fiber and is related to the strength of the bond between
the fiber and the matrix, or the stress at which the matrix begins to deform. If the fiber
length is greater than about 15 , the fiber behaves almost as if it was continuous. The
strength of the composite can be estimated from relation 10.
= 1 + f (10)
Amount of fibers is another factor which controls the strength and stiffness of composite. As
we expect from rule of mixture the greater volume fraction of fibers means the more
strength and stiffness of the composite. However, the maximum volume fraction is about
80%, beyond which fibers can no longer be completely surrounded by the matrix [1].
Orientation of fibers also could change the amount of strength and stiffness of the
composite. The reinforcing fibers may be introduced into the matrix in a number of
orientations. Short, randomly oriented fibers having a small aspect ratio are easily
introduced into the matrix and give relatively isotropic behavior in the composite.
In most FRP composites the fibers are strong, stiff and lightweight. If the composite is to be
used at elevated temperatures, the fiber should also have a high melting temperature. Thus
the specific strength and modulus of elasticity of the fiber are important characteristic. In
specific characteristic, density has an important role. The lighter the material, the more
strength and stiffness. Relation 11 and 12 show the specific strength and modulus. Where
is density of the composite.
= (11)
= (12)
Figure 5. Effect of fiber orientation on the tensile strength of FRP composite. The most strength obtains
where the force is applied along the fibers and the least is where the force is applied perpendicular to
the fibers.
50
ASTM Original Asid
Standard immersed
Sample(s)
Figure 6. Figure6. Comparison of Flexural strength of FRP specimens (ASTM standard, Original or non
immersed and immersed samples). The original samples were stored aged for 15 years. And the
immersed samples are the original ones which were immersed at 50oc for different intervals.
148 Polyester
By comparison between standard and tested specimens it is revealed that the flexural
strength shows 10% decrease after 15 years storage aging. By immersion at 50oC in acid the
samples showed gradual deterioration in flexural strength. The results show that storage
aging and acid immersion effect on flexural strength is much less than the effect on tensile
strength.
The bending displacements corresponding to the flexural strength of the samples (i.e.
original, 7, 14, and 21 days immersed samples) at 50oC are also shown in figure 7. Acid
immersion caused the gradual decrease of bending displacement similar to the tensile and
flexural properties. It seems that penetration of acid made the samples less flexible and more
rigid.
25
20
20
Displasment (mm)
17
15 12
10 9
5
0
Original 7 14 21
Times of immersion (days)
Figure 7. Displacement of original and acid immersed samples due to flexural test. The more immersed
samples, the less flexibility and displacement.
When the FRP samples are in contact with the mineral acid solution environment, acid
diffuses into the macromolecule of the polymer, degrades the matrix, reinforcements and
interfaces. The absorption of acid at different times and temperatures accelerated the rate of
aging. Thus reduction of mechanical properties such as tensile strength, flexibility, modulus
of elasticity and elongation at break occurred. The effect of this highly destructive process is
evidenced by swelling, discoloration and decrease in the mechanical properties of the
samples. Chemical attack of polyester matrix by the acid solution environment led to
hydrolysis of esters groups of the matrix. Since these groups are located in the chain
backbone of the polymer, chain scission occurs. The decrease in molecular weight due to
this scission can lead to the reduction in the mechanical properties.
Also the reduction in the flexural strength of the original samples is explained by
weathering and thermal degradation. Although the specimens were not suffered by direct
exposure of sun light, UV light exists in the environment and could harm the matrix.
Weathering is initiated by the absorption of UV radiation by chromophores and in the
activation of excited states in the macromolecules. When a polyester composite is exposed to
Fibre Reinforced Polyester Composites 149
a source of energy (solar or thermal) the absorbed energy by the polymer matrix results in
the formation of free radicals. Once free radicals have been produced, reaction with oxygen
generates hydroperoxides. These hydroperoxides can dissociate further to produce a series
of decomposition products including aldehydes and ketones. Decrease of the flexural
properties is due to the formation of these products and scissoring of polymer
macromolecules. Regarding to the storage period of specimens, heat, moisture and air-born
pollution all influence the mechanism of degradation [6].
= + (13)
But it does not usually do this. We have already seen that if the length of the fibers is less
than , they will not fracture. And if they do not fracture they must instead pull out as the
crack opens (Figure 8). This gives a major new contribution to the toughness. Where the
matrix shear strength is , then the work done in pulling a fiber out of the fracture surface
is given approximately by relation 14.
= = (14)
The number of fibers per unit crack area is 4 (because the volume fraction is the
same as the area fraction on a plane perpendicular to the fibers). So the total work done per
unit crack area is:
150 Polyester
= = (15)
This assumes that is less than the critical length . If is greater than the fibers will not
pull out, but will break instead. Thus optimum toughness is given by setting = in
equation 15 to give :
= (16)
The equation says that, to get a high toughness, you should use strong fibers in a weak
matrix (though of course a weak matrix gives a low strength). This mechanism gives CFRP
and GFRP a toughness (50 kJ m2) far higher than that of either the matrix (5 kJ m2) or the
fibers (0.1 kJ m2); without it neither would be useful as an engineering material [7].
Failure of polyester composites may occur because of cumulative damage to the matrix,
interfacial separation with the fibers, chemical attack of the fibers or a combination of two or
more of these processes. The net effect is loss of stiffness and mechanical integrity. This
section examines the degradation of composite materials and constituent components (i.e.
fiber, matrix, fiber-matrix interface and interphone) as a result of exposure to aggressive
environments.
P + O2 PO
All polyesters contain these free radicals due to their polymerization and processing history.
However, the concentration of free radicals can be significantly increased by interaction
with light, ionizing radiation or the presence of transition metals. Once formed the peroxide
radicals undergo slower propagation reactions that breakdown the polyester chains. The
overall degradation process will normally involve a relatively long induction period during
which little degradation is observed. At the end of this period there is a rapid increase in
degradation leading to a significant reduction in the mechanical properties of the polyester.
This induction period is temperature sensitive and is reduced significantly at elevated
temperatures. The induction period of the degradation process can normally be regarded as
the serviceable lifetime of the polyester.
Other physical changes can occur in the polyesters at elevated temperatures, one of the most
common being thermal expansion. Thermal expansion is reversible and in general does not
significant affect the life expectancy of a polymer. However, in polyester composites the
mismatch between the thermal expansion of the polyester matrix and the fibers may cause
thermo-mechanical degradation during thermal cycling.
4.2. Weathering
Weathering or more specifically photo-oxidation of polyesters refers to the chemical and
physical changes that occur when radiation is absorbed by a polymer. Photo-degradation is
initiated by solar radiation, which results in the absorption of UV radiation by
chromophores and in the activation of excited states in macromolecules. However, other
climatic quantities such as heat, moisture and air-born pollution all influence the
mechanisms of degradation and the subsequent results of ageing.
152 Polyester
When a polymer is exposed to solar radiation the energy absorbed by the polymer results in
the formation of free radicals within the polymer by the dissociation of the C-H bonds in the
polymer chains.
PH P + H
The extent of this chemical reaction depends on the radiation exposure that is the quantity
of ultraviolet light (<350nm) to which it is exposed. Once free radicals have been produced,
reaction with oxygen generates hydro peroxides (POOH).
P + O2 POO
POO + PH POOH + P
These hydro peroxides can dissociate further to produce a series of decomposition products
including aldehydes and ketones. The presence of these carbonyl groups in a degraded
polyesters can be used as a chemical index for degradation. When these free radicals
formed, it can continue to react via propagation reactions long after the initial UV exposure
has ended. Termination of these free radical reactions is normally achieved through the
reaction of pairs of free radicals.
P + P P-P
The formation and propagation of free radicals in itself does not serious affect the
mechanical properties of the polymer, as they do not significantly alter the long-chain
nature of the polymer molecules. Degradation of the mechanical properties occurs because
the free radicals produced are highly unstable and readily undergo chain scission reactions.
This results in the formation of two smaller polymer chains which each of them is a free
radical and they are capable of further reactions. These reactions continuo and go on and on.
Fortunately the intensity of the UV radiation decreases with increasing depth in the
material, so that the reaction tends to be a near surface process. Since oxygen is involved in
the reaction process, there is an important balance between UV radiation and oxygen
diffusion, and of course temperature since that will also determine the kinetics of reaction
and the transport of reactive species.
The reduction in molecular weight consequent upon chain scission can lead to a reduction of
toughness and fracture strain. Stress is known to accelerate the chain scission process and
also to enhance the rate of fluid uptake.
Fibre Reinforced Polyester Composites 153
As the deformation region develops, further localized deformation is induced. The growth
and coalescence of such deformed nuclei create a narrow plastic zone. In the presence of
dilatational stress, voids develop. This voided structure is considered the precursor of the
fibrillated craze structure that ultimately leads to failure. The environment accelerates the
craze formation process by local plasticization, for example enhancement of the local relative
movement of molecular chains by reduced intermolecular interaction between chains.
The intensity of ionizing radiation on the earths surface is not normally high enough to
significantly affect most plastics, hence radiation degradation is only occurred in connection
with nuclear plants and where radiation is used for applications such as medical x-rays,
sterilization or cross-linking.
changes and diminished performance. Capillary action along the fibers can account for a
significant proportion of initial moisture uptake, although a chemically resistant matrix may
protect the fibers. Shrinkage of the resin away from the fibers during curing is a contributing
factor to the capillary effect. The effect of moisture is to cause hydrolytic breakdown of the
fiber matrix interface resulting in a loss in the efficiency of load transfer between the matrix
and the fiber reinforcement.
The moisture absorption kinetics of polymer systems differs widely between resin systems
and also changes with chemical ageing. The glass transition temperature for a typical
polyester resin decreases by approximately 15-20C for a 2% moisture weight gain. This
reduction in Tg is induced by softening or plastization of the polymer matrix and in some
cases by loss of organic additives through leaching to the surrounding media. It is advised
that when using FRP products be sure that the maximum operating temperature is at least
30-40C below the Tg of the polyester (taking into account moisture effects). Table 7 shows
the variation of Tg with moisture content for a composite E glass / polyester[8].
Although the process of moisture absorption within the surface layers occurs almost
immediately on contact with the environment, moisture diffusion into the bulk material is
usually a slow process. It may take weeks to months before a substantial amount of
moisture has been absorbed by the composite, and considerably longer periods (i.e. 1-2
years) before the material is saturated. The rate of moisture uptake by a FRP composite is
dependent on the temperature, relative humidity, exposure time and mechanical load. At
elevated temperatures, the rate of moisture uptake and material property degradation is
accelerated. Also the presence of tensile loads accelerates moisture uptake by opening
existing internal cavities or voids, and by contributing to micro-crack formation. A FRP
composite containing micro-cracks will absorb considerably more moisture than an
undamaged laminate. Exposing the wet composite to sub-zero temperatures can further
exacerbate this process.
Degradation of E-glass fibers in water can be mainly attributed to leaching of alkali oxides
(sodium and potassium oxide) from the fiber surface resulting in the formation of surface
micro-cracks, which act as stress concentrators. The loss of strength can be expected to be
permanent at all conditioning temperatures and exposure times. The presence of Na+ ions in
solution slows down the exchange of alkali ions, such as NaOH-, and restricts entry of Cl-
ions into the silic acid network. Chloride ions slow the degradation process, although only
slightly. Under the influence of humidity or water the fiber forms a water skin in which the
alkali ions (e.g. NaOH-) are leached from the fiber surface and replaced by protons (H+). The
thickness of the silic acid structure or skin increases with exposure time and is dependent on
the temperature and humidity of the surrounding environment. The water surrounding the
glass fibers evolves into an aggressive alkali solution as the alkali ions dissolve out of the
156 Polyester
glass, slowly decomposing the glass fibers. Increasing the alkali content of the glass tends to
reduce environmental attack from water and alkali solutions. Drying of the composite will
remove most of the skin of water adjacent to the fiber, but a small permanent layer with
retained water will still remain, and the mechanical properties of the fiber will be
permanently degraded. Below reaction shows the chemical reaction of water with a fiber
glass. Where R is Na, K, Ca, Mg, Al. As with moisture effects, acid and alkali degradation
processes are accelerated at elevated temperatures.
+ +
In the case of acid environment, the acid come into contact with glass fibers, ionic exchange
occurs between the metallic cations (e.g. Na+ ions) at the glass surface and the hydrogen
ions in the acid solution, resulting in leaching of sodium, potassium, calcium, magnesium,
boron and aluminum from the outer layer or sheath of the fiber. The dissolution of the
supporting network results in a slight enlargement of the fiber diameter and shortening of
the fiber length as longitudinal stresses relax, which is resisted by the unaffected core. As
the outer layer becomes depleted, tensile stresses imposed by the core of the fiber build up,
which significantly decreases the load capability of the fiber and eventually leads to cracks.
Below reaction shows the chemical reaction of acid with a fiber glass [9].
+ +
Figure 10(a) shows micrograph of fracture section of the FRP sample before acid immersion
at ambient temperature. From this figure one may notice the closely adherence of fibers. A
few fibers are pulled out from matrix when tensile stress was applied. Figure 10(b) shows
micrograph of fracture section of the FRP sample after 21 days acid immersion at 35oC
temperature. It is clear that when tension was applied all the fibers were pulled out of
matrix because of the loss bond between matrix and fibers. This figure confirms destructive
effect of the acid on the FRP composite structure and shows how acid penetration
deteriorates fibers/matrix interfacial bond. During the acid absorption of the interphase, acid
solution penetrated into the free space of polymer which induced more new cavities and
cracks, and washed out the fibers surface. Thus the interphase gradually is damaged and the
cohesive bonds between fiber glass surfaces and the matrix has been retarded. In addition
to destructive effect of acid, aging of the specimens intensified the amount of damage
imposed to the samples [6].
In the case of alkali attack, the chemical reaction involves a breakdown of the silica network
by hydroxide (OH-) ions and eventually dissolution of all the species in the fiber glass. The
glass fibers gradually lose weight and strength when they are in contact with strong alkalis.
Immersion in weak caustic solutions at room temperature can result in strength reductions
of 30% within 2 weeks. The rate of degradation of glass fibers to alkalis is not determined by
the rate of diffusion, but by the active dissolution of the SiO2 network. The loss of mass is
proportional to time. Acid corrosion resistant glass is only slight more resistant to strong
alkalis. Below reaction shows the chemical reaction of alkali with a fiber glass. Where R is
Na, K, Ca, Mg and Al.
Fibre Reinforced Polyester Composites 157
Figure 10. Fracture section of the aged FRP sample before acid immersion (a), after 21 days acid
immersion at 35oC temperature (b).
Si O R + H O Si O R + OH
Si O Si + OH Si OH Si + O
It must be mentioned that the resistance of glass fibers can be improved by modifying the
chemical composition. Table 8 shows corrosion resistance comparison between different
steels and FRP in hostile environments. It is obvious that FRP materials are resistible in all
corrosive environments .However, the amount of resistibility depends on the kind of
polyester and fiber, method of production and the grade of hostility.
= unaected = corroded
Material Dilute Conc. Dilute Conc. Dilute Chloride Dilute
H2SO4 H2SO4 HCl HCl HNO3 Salts NaOH
FRP (laminate)
Carbon steel (1020)
Stain less (316)
Hastelloy (C)
Table 8. Comparison of corrosion resistance of different materials in corroded environments.
158 Polyester
The dielectric properties of FRP means that it can be used safely where electrical
conductivity cannot be tolerated. The anisotropic nature of FRP (different physical
properties in different directions) enables the engineer to align the fiber reinforcement with
the principal strain field, thus making the equipment stronger and lighter than a
corresponding steel fabrication.
The applications of composites are not limited to fiber reinforced plastics, either. In another
important application, and by no means the only other example, polymer concrete bridge
deck overlays provide chloride protection for bridge deck reinforcement steel while
restoring roadway profile, durability, and ride quality. The overlays can be placed under a
variety of extreme environmental conditions and, as a result, two to four-hour cure times are
achievable allowing a rapid return to public traffic.
Whether it is the material itself or its corrosion resistance, all of these advantages translate
into better engineered systems that perform better, last longer, and cost less.
Likewise, metal properties may vary considerably depending on the particular alloy or the
manner in which the metals have been annealed or pre-processed.
Reinforced composites are not as stiff as most metals, and obviously can be limited in
applications requiring high modulus of elasticity. FRP also does not display other favorable
properties of metals such as ductility or malleability. On the other hand, FRP features a low
density, which can often give a good strength to weight ratio, which is important in
transportation and many structural applications. FRP is also a relatively good thermal as
well as an electrical insulator. Fabrication or repairs can be made easily, and without the
need for arc welding in hazardous areas.
Table 9 compares the principal material properties of FRP to those of various metals. The
light weight (density) and the strength to weight ratio of FRP are clear advantages in
transportation and in handling. The thermal conductivity is a clear advantage when storing,
using, or transporting fluids at elevated temperature. With a thermal conductivity only
1/187 that of carbon steel and 1/900 that of aluminum, heat loss is much less and the hazard
that hot equipment poses for workers is reduced.
Fibre Reinforced Polyester Composites 159
The reduced tensile strength, coefficient of thermal expansion (at twice that of carbon steel),
and modulus of elasticity introduce design considerations that may, at first, appear to be
disadvantages to design engineers more familiar with steel, but are, in fact, advantages. The
coefficient of thermal expansion (at twice that of carbon steel) may be seen as a
disadvantage in the case of applying an FRP liner to a steel substrate, e.g. as in relining a
steel tank, but with a modulus 1/30th that of steel, resultant thermal forces in a piping
system are only 1/15th that of carbon steel (because of the lower modulus of elasticity). An
actual calculation is necessary to weigh this advantage for thrust blocks in restrained piping
systems, since the wall thickness and pipe size also enter into the calculation of the thrust
force. Conversely, the lower modulus of elasticity means that pipe guides will be closer
together due to the earlier onset of elastic instability [10].
The first structural composite aircraft components, which were introduced during 1950-60,
were made from glass fiber reinforced plastics. These components included the fin and the
rudder of Grumman E-2A, helicopter canopies, frames, radomes, fairings, rotor blades, etc.
Due to high strength and stiffness combined with low density, composites like boron fiber
160 Polyester
reinforced plastics (BFRP) and carbon fiber reinforced plastics (CFRP) were preferred
instead of aluminum for high performance aircraft structures. For lightly loaded structures,
aramid fiber reinforced plastics (AFRP) which possess low density, have been used. The use
of AFRP continues to be restricted to the lightly loaded structures due to the fact that
although these fibers possess high tensile strength, they have very low compressive
strength. For light aircraft and lightly loaded structural components, glass fiber reinforced
plastics (GFRP) has become one of the standard materials. Over the years, use of composite
materials has also increased from few small access panels and canopy frames to almost
complete airframe surfaces thereby providing weight savings leading to improved
performance, reduced drag and also improved durability and corrosion resistance.
Consequently, now-a-days, composite materials like GFRP, CFRP and AFRP have become
standard materials for flight control surfaces, engine cowlings, fairings, radomes, landing
gear doors, floor panels, fan ducts, etc. in aircraft application.
FRP composite materials are being used for different helicopter components as well. Use of
advanced FRP composites in helicopter application started way back in 1959 with the
development of Optimum Pitch Blade for the XCH-47 twin rotor helicopter of Vertol
Aircraft Corporation. There-after, use of composites in helicopter application has been
progressively extended to various parts, which include main & tail rotor blades, stabilizers
and fuselage portions. Experience has shown that GFRP main rotor blades have a service life
of around 10,000 hours as compared to blades with steel/titanium spars, which have a life of
around 1000- 2000 hours.
Flex-beam CFRP rotors are also in use on McDonnell Douglas MD 520N/MD 900 helicopters
with NOTAH (No Tail Rotor) system. Composite blades can be designed to be fail-safe and
unlike metal blades they do not require frequent inspections for defects. In addition, blade
and rotor system efficiencies have been improved due to tailorability of composites. Their
longer life and reduced in-service inspection requirements make them very attractive and
cost effective.
By replacing conventional cast iron or sheet steel box with Halyester (a glass fiber-reinforced
polyester) containers, the danger of personal contact with electrical voltage has been
considerably reduced. As well as its dielectric properties, Halyester is said to be used both
indoors and outdoors.
weight and high dielectric properties. It doesn't require any painting and very easy to
handle and easily repairable if there is any problem.
In FRP storage tanks generally, the tank shell is filament wounded and top and bottom is
hand press molded. Usually tank design is based on international standards like BS-4994,
ASTM-D 3299 and ASME section ten.
with the advantages like corrosion resistance, longer life, low maintenance, ease in
workability, fire retardancy etc.
Natural fibers, as a substitute for glass fibers in FRP composite components, have gained
interest in the last composite ceiling panel decade, especially in the housing sector. Fibers
like flax, hemp or jute are cheap, have better stiffness per unit weight and have a lower
impact on the environment. Structural applications are rare since existing production
techniques are not applicable and availability of semi-finished materials with constant
quality is still a problem.
Some example of FRP fans are in cooling towers for power plants, mine ventilation for air
heat exchanger, diesel locomotive radiator cooling fan and textile mill humidifiers. The
performance of all the above fans was tested in actual field conditions with an efficiency
differential as high as 25% over conventional fans with aluminum impellers.
Also application of these impellers in corroded environment such as ventilating the acidic
gas and fumes is so desirable. Because if the rate of corrosion and cost of FRP impellers are
being considered in comparison with stainless steels and titanium impellers, the FRP
impellers will be more beneficial than the latter.
However there are opportunities for advanced composites in specific components in the
commercial automotive sector. In specialty vehicles of several types, produced in small
numbers advanced composite materials have an opportunity to demonstrate their
performance benefits, apart from the requirements of the competitive marketplace.
Fibre Reinforced Polyester Composites 163
The composite industry worldwide is investing in process improvements for the molding of
polymer composites using forms of conventional E-glass in mid-level performance resins,
both thermoplastic and thermoset. Automobiles segment of composites accounts for about
50% of the thermoplastic and 24% of the thermoset composite market in the world. Glass-
reinforced thermoplastic polymer is a promising material for weight reduction because of
the relatively low cost of the fiber, its fast cycle time and its ability to facilitate parts
integration. Carbon fiber reinforced polymer is another candidate but will require
breakthroughs in cost and manufacturing techniques to be cost effective for high volume
production.
industry and as antiskid trench cover installations in paper mills. In the metal refining
industry, it is used for aisles between cells. In food processing operations where acid
conditions exist, FRP grating is employed as floor mats. It has also found use in fencing off
high-voltage transformers. FRP grating has approximately one-fourth the specific gravity of
steel and roughly two-thirds that of aluminium. In general, fibreglass grating has many of
the qualities of metal plus several superior advantages. Gratings can be fabricated from a
variety of resins on the market. The particular resin used will depend on the specific
corrosion environment for which it is intended. Manufacturers will supply samples of
grating for immersion tests or test sections can be installed on the site. Fibreglass grating is
available in a plain top surface or a surface that has deeply imbedded grit particles. The
latter design is employed in applications where maximum non skid features are required.
Particles are fabricated into the structure and, as such, are not worn away after constant
exposure to corrosive environment and continuous wear. The material is imbedded with
angular silica particles during the laying up process. The product is essentially a matrix of
polyester resin. Resin wears faster than the silica grit so the grit profile always protrudes
above the resin base. This results in very high friction coefficients, even after many years of
service.
6. Conclusion
FRP composites are composed of two materials or phases joined or connected to each
other in such a way to give a combination of properties that cannot be attained
otherwise. The properties of the individual components, the relative amount of phases,
the orientation of various components, the degree of bonding between the phases, the
size, shape and distribution of the discontinuous phase are very important in
determining the properties of composite.
Fiber-reinforced polyester composites provide improvements in strength, stiffness and
toughness. They also could have corrosion resistance in different hostile environments.
By using different glass fibres electrical resistivity is controllable also. Fibres typically
have low densities, giving high specific strength and specific modulus, but they often
are brittle. Fibres can be continuous or discontinuous. Discontinuous fibres with high
aspect ratio produce better reinforcement.
Fibres are introduced to the matrix in a variety of orientations. Random orientations
and isotropic behaviour are obtained using discontinuous fibres; unidirectional fibres
produce composites with anisotropic behaviour, with large improvements in strength
and stiffness parallel to the fibre direction. Properties can be tailored to meet the
imposed loads by orienting the fibres in multiple directions.
Although the FRP composites are resistant in hostile environments, such environment
as well as acidic and alkali ones could deteriorate the interface of fibres and matrix if
they contact with the interface directly. So the mechanical properties could decrease if
the specimens are in contact with hostile environments intensively.
FRP composites have different application in construction, aerospace, automotive,
sports and other industries.
Author details
Salar Bagherpour
Islamic Azad University, Department of Materials Science and Engineering, Najafabad-Branch, Iran
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